Cosmetic composition for the hair with a waxy effect, in aerosol form

ABSTRACT

The disclosure relates to a cosmetic composition for the hair, packaged in an aerosol device, comprising polyols in high concentration together with anionic fixing polymers. It further relates to a cosmetic method for the hair comprising the application of this composition to the hair, and to its use for imparting a waxy effect to the hair.

[0001] This application claims benefit of U.S. Provisional ApplicationNo. 60/434,677, filed Dec. 20, 2002.

[0002] The present disclosure relates to a cosmetic composition for thehair, packaged in an aerosol device, comprising polyols in highconcentration together with anionic fixing polymers. It further relatesto a cosmetic method for the hair comprising the application of thiscomposition to the hair, and to its use for imparting a waxy effect tothe hair.

[0003] For the purposes of the present disclosure, “cosmeticcompositions for the hair” are understood as meaning hair fixing and/orholding compositions, hair care compositions, hair conditioningcompositions, such as compositions for imparting softness to the hair,or hair make-up compositions.

[0004] “Composition with a waxy effect” is understood as meaning a pastycomposition for holding and/or fixing the individual hairs together bymeans of a certain slicking or greasing effect without the hardeningeffect of fixing sprays, while at the same time preserving the naturalgloss of the hair.

[0005] The cosmetic composition for hair according to the disclosure canbe used in a rinsed or leave-in application.

[0006] Hair styling compositions, such as lacquers and sprays, packagedin the form of an aerosol spray can be generally made up of a liquidphase comprising at least one film-forming polymer in a cosmeticallyacceptable alcoholic or aqueous-alcoholic medium, and a propellant,which can be a gas liquefied under reduced pressure or dissolved in theliquid phase.

[0007] The majority of hair styling products with a waxy effect arepresented in the form of a more or less viscous paste which is appliedto the hair by hand. In general, these products are packaged in tubes orin containers fitted with a lid.

[0008] It would be desirable to present this type of hair stylingproduct in packaging that is easier to use.

[0009] In the hair product art, attempts are being made to manufactureaerosol lacquers containing reduced amounts of volatile organiccompounds, such as ethanol, essentially for ecological reasons, while atthe same time preserving good hair shaping and holding properties. Aproblem that may be posed by the search for such a product is to findcosmetic compositions that impart a waxy effect to the hair withoutexhibiting the disadvantages expressed above.

[0010] Surprisingly and unexpectedly, it has been discovered by thepresent inventors that it is possible to impart a waxy effect to thehair without detracting from its cosmetic properties, such as itsnatural softness, by using polyols in high concentration combined withanionic fixing polymers, packaged in aerosol form.

[0011] The present disclosure thus relates to a cosmetic composition forthe hair, packaged in an aerosol device, comprising:

[0012] a) at least one anionic fixing polymer, present in an amountranging from 0.5% to 10% by weight, based on the total weight of theaerosol composition,

[0013] b) at least one polyol with a molecular weight less than 500,present in an amount greater than 15% by weight, based on the totalweight of the aerosol composition,

[0014] c) an aqueous-alcoholic or aqueous medium comprising at least 10%by weight of water, based on the total weight of the aerosolcomposition, and

[0015] d) at least one propellant gas present in an amount greater thanor equal to 30% by weight, based on the total weight of the aerosolcomposition.

[0016] The present disclosure also relates to a hair styling methodusing the composition disclosed herein, packaged in an aerosol device.

[0017] Additional characteristics, features and advantages of thedisclosure are discussed in the description and the various Exampleswhich follow.

[0018] This disclosed combination of anionic fixing polymers and polyolsaffords aerosols with a low VOC content, for example, a VOC content lessthan or equal to 55%.

[0019] Without being bound by theory, it is believed by the presentinventors that the waxy effect of the compositions disclosed herein isobtained by combining at least one polyol with a molecular weight below500, in high concentration, with one or more anionic fixing polymers.The polyols provide the “slicking” or “greasy” aspect of waxes and theassociated anionic fixing polymers provide the “stiffening of thegrease”, which enables the hair to be shaped and held in the desiredconfiguration; waxes are completely absent from the formulation.

[0020] Anionic Fixing Polymer

[0021] The anionic fixing polymers useful in the compositions disclosedherein are polymers comprising groups chosen from derivatives ofcarboxylic, sulphonic and phosphoric acid groups, and have anumber-average molecular weight ranging from 500 to 5,000,000.

[0022] The carboxylic acid groups can be chosen from unsaturatedmonocarboxylic and dicarboxylic acid monomers such as those of theformula

[0023] wherein

[0024] n is an integer ranging from 0 to 10,

[0025] A₁ is a methylene group, which can be optionally joined to thecarbon atom of the unsaturated group, or to the adjacent methylene groupwhen n is greater than 1, via a heteroatom such as oxygen or sulphur,

[0026] R₇ is chosen from a hydrogen atom, phenyl and benzyl groups,

[0027] R₈ is chosen from a hydrogen atom, lower alkyl and carboxylgroups, and

[0028] R₉ is chosen from a hydrogen atom, lower alkyl groups —CH₂—COOH,phenyl and benzyl groups.

[0029] In the formula given above, a lower alkyl group may denote, forexample, a group having 1 to 4 carbon atoms, such as methyl or ethylgroups.

[0030] Non-limiting mention may be made of the following anionic fixingpolymers with carboxylic acid groups according to the presentdisclosure:

[0031] A) Homopolymers and/or copolymers of acrylic and/or methacrylicacid or their salts, for example, the products sold under the nameVERSICOL® E or K by ALLIED COLLOID and under the name ULTRAHOLD® byBASF, the acrylic acid/acrylamide copolymers sold in the form of theirsodium salts under the name RETEN 421, 423 or 425 by HERCULES, and thesodium salts of polyhydroxycarboxylic acids.

[0032] B) Copolymers of acrylic or methacrylic acid with a monoethylenicmonomer such as ethylene, styrene, vinyl esters and/or acrylic ormethacrylic acid esters, optionally grafted onto a polyalkylene glycolsuch as polyethylene glycol, and optionally crosslinked. Such polymersare described, for example, in French Patent No. 1 222 944 and GermanPatent Application No. 2 330 956, the copolymers of this type containingan optionally N-alkylated and/or hydroxyalkylated acrylamide unit intheir chain, such as those described for instance in Luxembourg PatentApplications Nos. 75370 and 75371, or marketed under the name QUADRAMERby AMERICAN CYANAMID. There may also be mentioned copolymers of acrylicacid and C₁-C₄-alkyl methacrylate and terpolymers of vinylpyrrolidone,acrylic acid and C₁-C₂₀-alkyl methacrylate, for example laurylmethacrylate, such as that marketed by ISP under the name ACRYLIDONE®LM, and methacrylic acid/ethyl acrylate/tert-butyl acrylate terpolymerssuch as the product marketed under the name LUVIMER® 100 P by BASF.

[0033] There may also be mentioned the methacrylic acid/acrylicacid/ethyl acrylate/methyl methacrylate copolymers in aqueous dispersionwhich are marketed under the name AMERHOLD® DR 25 by AMERCHOL.

[0034] C) Crotonic acid copolymers such as those comprising, in theirchain, at least one unit chosen from vinyl acetate and propionate unitsand optionally at least one other monomer chosen from allyl esters,methallyl esters, vinyl ethers and vinyl esters of linear or branched,saturated carboxylic acids with a long hydrocarbon chain, such as thosecontaining at least 5 carbon atoms, it optionally being possible forthese polymers to be grafted or crosslinked, or at least one othermonomer chosen from vinyl, allyl and methallyl esters of analpha-carboxylic or alpha-cyclic carboxylic acid. Such polymers aredescribed inter alia in French Patent Nos. 1 222 944, 1 580 545, 2 265782, 2 265 781, 1 564 110 and 2 439 798. Commercial products belongingto this class are the resins 28-29-30, 26-13-14 and 28-13-10 marketed byNational Starch.

[0035] D) Copolymers of mono-unsaturated C₄-C₈ carboxylic acids oranhydrides which may be selected from:

[0036] copolymers comprising (i) at least one entity chosen from maleic,fumaric and itaconic acids or anhydrides, and (ii) at least one monomerselected from vinyl esters, vinyl ethers, vinyl halides, phenylvinylderivatives and acrylic acid and its esters, the anhydride groups ofthese copolymers optionally being monoesterified or monoamidated. Suchpolymers are described for instance in U.S. Pat. Nos. 2,047,398,2,723,248 and 2,102,113 and GB Patent No. 839 805. Commercial productsfor example, may be those sold under the name GANTREZ® AN or ES by ISP.

[0037] copolymers comprising (i) at least one unit chosen from maleic,citraconic and itaconic anhydride units, and (ii) at least one monomerselected from allyl and methallyl esters, which may optionally compriseat least one group in their chain chosen from acrylamide,methacrylamide, alpha-olefin, acrylic acid ester, methacrylic acidester, acrylic acid, methacrylic acid and vinylpyrrolidone groups, theanhydride groups of these copolymers optionally being monoesterified ormonoamidated.

[0038] These polymers are described for example in French Patents Nos. 2350 384 and 2 357 241, assigned to L′Oréal.

[0039] E) Polyacrylamides comprising carboxylate groups.

[0040] Homopolymers and copolymers comprising sulphonic acid groups maybe polymers comprising groups chosen from vinylsulphonic,styrenesulphonic, naphthalenesulphonic and acrylamidoalkylsulphonic acidunits.

[0041] These polymers can be selected, for example, from:

[0042] polyvinylsulphonic acid salts with a molecular weight rangingfrom 1000 to 100,000, and copolymers with unsaturated comonomers such asacrylic or methacrylic acid and their esters, as well as acrylamide orits derivatives, vinyl ethers and vinylpyrrolidone.

[0043] polystyrenesulphonic acid salts such as the sodium salts sold forinstance, under the names Flexane 500 and Flexan® 130 by NationalStarch. These compounds are described in patent FR 2 198 719.

[0044] polyacrylamidesulphonic acid salts such as those mentioned inU.S. Pat. No. 4,128,631, for instance, thepolyacrylamidoethylpropanesulphonic acid sold under the name COSMEDIAPOLYMER HSP 1180 by Henkel.

[0045] The anionic polymers of the present disclosure can also bepolycondensation products comprising at least one polyurethane sequenceand at least one anionic group. These polycondensation products mayoptionally comprise a polysiloxane sequence. Among thesepolycondensation products, non-limiting examples include anionicpolyurethanes, such as those marketed by BASF under the name Luviset PURor Luviset Si PUR.

[0046] The anionic polymers of the present disclosure can also bepolymers with a silicone skeleton and hydrocarbon grafts, and polymerswith a hydrocarbon skeleton and silicone grafts, these polymersnecessarily having at least one anionic group in their structure. Thegrafts may be fixed to the skeleton via a macromonomer. The polymer VS30from 3M can be used as a polymer of this type.

[0047] As a further example, in the compositions according to thepresent disclosure, the anionic fixing polymer may be chosen fromhomopolymers and/or copolymers of acrylic and methacrylic acid and thesalts thereof, crotonic acid copolymers, copolymers of monounsaturatedC₄-C₈ carboxylic acids and/or anhydrides, polyacrylamides withcarboxylate groups, homopolymers and/or copolymers with sulphonic acidgroups, anionic polyurethanes and anionic grafted silicone polymers.

[0048] The hair styling composition contained in the aerosol deviceaccording to the present disclosure has a content of anionic fixingpolymers for example, ranging from 0.5 to 10% by weight, such as rangingfrom 1 to 8% by weight, for instance, ranging from 2 to 6% by weight,based on the total weight of the aerosol composition.

[0049] Polyol

[0050] The polyols used in the compositions disclosed herein may bemolecules comprising a C₃ to C₃₀ hydrocarbon chain which may optionallybe interrupted by at least one heteroatom and is substituted by at leasttwo hydroxyl groups. The molecular weight of the at least one polyolused herein is less than 500.

[0051] The hair styling composition contained in the aerosol deviceaccording to the present disclosure has a polyol content of greater than15% by weight, and may have a polyol content for example, ranging from15 to 55% by weight, such as, ranging from 15 to 40% by weight, forinstance ranging from 20 to 35% by weight, based on the total weight ofthe aerosol composition.

[0052] Propylene glycol, glycerol, isoprene glycol, neopentyl glycol,hexylene glycol and polyethylene glycols may be mentioned asnon-limiting examples of polyols which can be used herein.

[0053] In one aspect of the present disclosure, the hydrocarbon chain isnot interrupted by a heteroatom; the number of carbon atoms in thehydrocarbon chain may be, for instance, less than 10, such as less than8.

[0054] In another aspect of the present disclosure, the at least onepolyol is chosen from propylene glycol and glycerol.

[0055] In yet another aspect of the present disclosure, the polyol is aglycol, i.e. it contains at least two adjacent carbon atoms eachcarrying at least one hydroxyl group.

[0056] Aqueous-Alcoholic Medium

[0057] The hair styling composition contained in the aerosol devicedisclosed herein has a water content of at least 10% by weight, and mayhave a water content for example, ranging from 10 to 54.5% by weight,such as, ranging from 10 to 45% by weight, for instance, ranging from 10to 30% by weight, based on the total weight of the aerosol composition.

[0058] Propellant

[0059] According to the present disclosure, the propellant gas used maycomprise at least one gas that may or may not be soluble in thecomposition, such as dimethyl ether, fluorinated or non-fluorinatedhydrocarbons, the customary liquefied gases, or a mixture of thesepropellant gases. In one aspect of the disclosure, the propellant gas isdimethyl ether.

[0060] The hair styling composition contained in the aerosol deviceaccording to the present disclosure has a propellant gas content ofgreater than or equal to 30% by weight, and may have a propellant gascontent for example, ranging from 30 to 50% by weight, such as rangingfrom 30 to 45% by weight, for instance ranging from 30 to 40% by weight,based on the total weight of the the aerosol composition.

[0061] As an example, the composition may contain ethanol or isopropanolas the alcohol.

[0062] The hair styling composition can also comprise additives such assilicones in soluble, dispersed or microdispersed form, treating agents,hydrating agents other than the polyols of the invention, UV filters,acids, bases, plasticizers, solubilizers, preservatives, vitamins andprovitamins, colorants, pigments, anionic, cationic, non-ionic oramphoteric surfactants, cationic, non-ionic or amphoteric fixingpolymers, perfumes, corrosion inhibitors and mixtures thereof.

[0063] Those skilled in the art will take care to choose any additivesand their amount so that they do not detract from the properties of thecompositions of the present disclosure.

[0064] The compositions disclosed herein may be understood more clearlywith the aid of the non-limiting Examples below.

EXAMPLES Example 1

[0065] A 55% VOC aerosol spray was prepared which comprised thefollowing in g/100 g of active substance: PVP/VA: 1 Ultra Hold Strong(BASF): 4 Aminomethylpropanol: 0.48 Propylene glycol: 15 Glycerol: 15Perfume: 0.2 Water: 10.32 Alcohol: 14 DME: 40

[0066] PVPNA: marketed by BASF under the name Luviskol VA 64 Powder

Example 2

[0067] A VOC aerosol spray was prepared which comprised the following ing/100 g of active substance: Vinylpyrrolidone/Vinyl acetate (60/40): 42-amino-2-methyl-1-propanol: 0.4 Glycerol: 17.4 Dimethyl ether: 30Acrylic acid/Ethyl acrylate/n-tert-butylacrylamide: 3 Perfume: 0.3Propylene glycol: 11 Polydimethyl/methylsiloxane oxyethylene (18/5): 2.7Water: 10 Ethyl alcohol: 21.2

Example 3

[0068] A VOC aerosol spray was prepared which comprised the following ing/100 g of active substance: Vinylpyrrolidone/Vinyl acetate (60/40): 42-amino-2-methyl-1-propanol: 0.4 Glycerol: 17.3 Dimethyl ether: 30Acrylic acid/Ethyl acrylate/n-tert-butylacrylamide: 3 Perfume: 0.2Propylene glycol: 11 Polydimethyl/methylsiloxane oxyethylene (18/5): 2.7Water: 10 Ethyl alcohol: 21.4

Example 4

[0069] A VOC aerosol spray was prepared which comprised the following ing/100 g of active substance: Vinylpyrrolidone/Vinyl acetate (60/40): 32-amino-2-methyl-1-propanol: 0.3 Glycerol 17.4 Dimethyl ether: 33Acrylic acid/Ethyl acrylate/n-tert-butylacrylamide: 2 Perfume: 0.1Propylene glycol: 10 Polydimethyl/methylsiloxane oxyethylene (18/5): 2.7Water: 10.8 Ethyl alcohol: 20.7

What is claimed is:
 1. A cosmetic aerosol composition for hair, packagedin an aerosol device, comprising: a) at least one anionic fixing polymerpresent in an amount ranging from 0.5% to 10% by weight, based on thetotal weight of the aerosol composition, b) at least one polyol with amolecular weight less than 500, present in an amount greater than 15% byweight, based on the total weight of the aerosol composition, c) anaqueous-alcoholic or aqueous medium comprising at least 10% by weight ofwater, based on the total weight of the aerosol composition, and d) atleast one propellant gas in an amount greater than or equal to 30% byweight, based on the total weight of the aerosol composition.
 2. Thecomposition according to claim 1, wherein the at least one anionicfixing polymer is chosen from homopolymers and/or copolymers of acrylicand methacrylic acid and the salts thereof, crotonic acid copolymers,copolymers of monounsaturated C₄-C₈ carboxylic acids and/or anhydrides,polyacrylamides with carboxylate groups, homopolymers and/or copolymerswith sulphonic acid groups, anionic polyurethanes and anionic graftedsilicone polymers.
 3. The composition according to claim 1, wherein theat least one anionic fixing polymer is present in an amount ranging from0.5 to 10% by weight, based on the total weight of the aerosolcomposition.
 4. The composition according to claim 3, wherein the atleast one anionic fixing polymer is present in an amount ranging from 1to 8% by weight, based on the total weight of the composition.
 5. Thecomposition according to claim 4, wherein the at least one anionicfixing polymer is present in an amount ranging from 2 to 6% by weight,based on the total weight of the aerosol composition.
 6. The compositionaccording to claim 1, wherein the at least one polyol is present in anamount ranging from 15 to 55% by weight, based on the total weight ofthe aerosol composition.
 7. The composition according to claim 6,wherein the at least one polyol is present in an amount ranging from 15to 40% by weight, based on the total weight of the aerosol composition.8. The composition according to claim 7, wherein the at least one polyolis present in an amount ranging from 20 to 35% by weight, based on thetotal weight of the aerosol composition.
 9. The composition according toclaim 1, wherein the at least one polyol is a glycol.
 10. Thecomposition according to claim 1, wherein the at least one polyol ischosen from propylene glycol, glycerol, isoprene glycol, neopentylglycol, hexylene glycol and polyethylene glycols.
 11. The compositionaccording to claim 10, wherein the at least one polyol is chosen frompropylene glycol and glycerol.
 12. The composition according to claim 1,wherein the polyol comprises a hydrocarbon chain which is notinterrupted by a heteroatom.
 13. The composition according to claim 12,wherein the number of carbon atoms in the hydrocarbon chain is less than10.
 14. The composition according to claim 13, wherein the number ofcarbon atoms in the hydrocarbon chain is less than
 8. 15. Thecomposition according to claim 1, wherein the medium is anaqueous-alcoholic medium comprising an alcohol chosen from ethanol andisopropanol.
 16. The composition according to claim 1, wherein themedium comprises from 10 to 54.5% by weight of water, based on the totalweight of the composition.
 17. The composition according to claim 16,wherein the medium comprises from 10 to 45% by weight of water, based onthe total weight of the composition.
 18. The composition according toclaim 17, wherein the medium comprises from 10 to 30% by weight ofwater, based on the total weight of the composition.
 19. The compositionaccording to claim 1, wherein the at least one propellant gas is presentin an amount ranging from 30 to 50% by weight, based on the total weightof the composition.
 20. The composition according to claim 19, whereinthe at least one propellant gas is present in an amount ranging from 30to 45% by weight, based on the total weight of the composition.
 21. Thecomposition according to claim 20, wherein the at least one propellantgas is present in an amount ranging from 30 to 40% by weight, based onthe total weight of the composition.
 22. The composition according toclaim 1, wherein the at least one propellant gas is dimethyl ether. 23.The composition according to claim 1, further comprising at least oneadditive chosen from silicones in soluble, dispersed or microdispersedform; treating agents; hydrating agents other than the polyols of theinvention; UV filters; acids; bases; plasticizers; solubilizers;preservatives; vitamins and provitamins; colorants; pigments; anionic,cationic, non-ionic or amphoteric surfactants; cationic, non-ionic oramphoteric fixing polymers; perfumes; and corrosion inhibitors.
 24. Acosmetic method for styling hair comprising, applying to hair acomposition comprising: a) at least one anionic fixing polymer presentin an amount ranging from 0.5% to 10% by weight, based on the totalweight of the aerosol composition, b) at least one polyol with amolecular weight less than 500, present in an amount greater than 15% byweight, based on the total weight of the aerosol composition, c) anaqueous-alcoholic or aqueous medium comprising at least 10% by weight ofwater, based on the total weight of the aerosol composition, and d) atleast one propellant gas in an amount greater than or equal to 30% byweight, based on the total weight of the aerosol composition, whereinthe composition is packaged in an aerosol device.
 25. An aerosol devicefor imparting a waxy effect to hair, wherein the aerosol device containsa composition comprising: a) at least one anionic fixing polymer presentin an amount ranging from 0.5% to 10% by weight, based on the totalweight of the aerosol composition, b) at least one polyol with amolecular weight less than 500, present in an amount greater than 15% byweight, based on the total weight of the aerosol composition, c) anaqueous-alcoholic or aqueous medium comprising at least 10% by weight ofwater, based on the total weight of the aerosol composition, and d) atleast one propellant gas in an amount greater than or equal to 30% byweight, based on the total weight of the aerosol composition.